JPH01265511A - Organometallic compound supported on a carrier for use in vapor phase growth and an organometallic compound supply device for vapor phase growth using the same - Google Patents

Abstract

PURPOSE:To make it possible to feed vapor growth organic metal compound, having a predetermined reproducibility, to a vapor growth device by a method wherein an organic metal compound which is a solid at ordinary temperature and sued for vapor growth is applied to the carrier which is inert to the solid organic metal compound. CONSTITUTION:An organic compound is coated on a carrier which is inert against a solid organic metal compound, to be used for a vapor growth operation, at the normal temperature. as an organic metal compound, trimethylindium, demethylchloroindium, and cyclopentadienylindium are used. Pertaining to a carrier, one which has a wide specific surface area is desirable, and the carrier having the microscopic recesses and projections of about 100-2000mum or having a number of pores on the carrier itself is better than the carrier having smooth surface. Rasching ring helipac and the like are sued as the carrier. As a result, the supply of the vapor phase organic metal compound, having a constant reproducibility, into a vapor phase growing device can be made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a carrier-supported organometallic compound used for vapor phase growth and an organometallic compound supply apparatus for vapor phase growth using the same. More specifically, an organic metal compound that is solid at room temperature (hereinafter sometimes referred to as a solid raw material for vaporization) is coated on a carrier that is inert to the organic metal compound and is used for vapor phase growth. The present invention relates to an organometallic compound and an organometallic compound supply device for vapor phase growth using the same.

<Prior Art> In recent years, organometallic compounds have been used in the electronic industry, for example, as raw materials for compound semiconductors.

When the organometallic compound is used in the electronics industry, a carrier gas such as hydrogen gas is usually blown into contact with the organometallic compound, and the saturated vapor of the organometallic compound is introduced into a vapor phase growth apparatus for use.

In this case, if the organometallic compound is a liquid at its operating temperature, the liquid organometallic compound is filled into a container equipped with a capillary tube that allows a carrier gas to be bubbled through the organometallic compound as shown in FIG. At the same time, by blowing and bubbling a carrier gas through a thin tube, saturated vapor of the organometallic compound corresponding to the temperature at that time can be immediately obtained.

However, in the case of organometallic compounds that are solid at normal temperature (room temperature), unlike liquids, even when carrier gas is blown into the solid organometallic compound, a flow path is formed through which the carrier gas passes, or vaporization occurs. As a result, the solid organometallic compound with a small particle size is deposited at the bottom of the container, and as a result, sufficient contact between the solid organometallic compound and the carrier gas cannot be obtained, making it difficult to supply a stable concentration of the organometallic compound to the vapor phase growth apparatus. It has the fatal drawback of not being able to.

<Problems to be Solved by the Invention> In view of the above circumstances, the present inventors aimed to find a method that uses a solid organometallic compound at room temperature and can obtain a certain reproducible amount of evaporation of the organometallic compound. As a result of extensive study, we found that if a solid organometallic compound is coated on a carrier that is inert to the solid organometallic compound at room temperature in advance and used as a solid raw material for vaporization for vapor phase growth, it is possible to achieve the above objectives. They have discovered that all of these problems can be solved, and have completed the present invention.

Means for Solving the Problems> That is, the present invention is characterized in that (1) a carrier that is inert to an organometallic compound that is solid at room temperature used for vapor phase growth is coated with the organometallic compound; In an organometallic compound supply device for vapor phase growth, which comprises a carrier-supported organometallic compound used for vapor phase growth, and (2) a container that stores the organometallic compound that is solid at room temperature and sublimates the solid organometallic compound for vaporization. A carrier gas inlet is provided at the top of the container, and a carrier gas outlet is provided at the bottom of the container, and a carrier-supported organometallic compound in which the organometallic compound is coated on a carrier inert to the organometallic compound for vaporization is placed in the container. An object of the present invention is to provide an organometallic compound supply device for vapor phase growth, which is characterized in that it is filled with organic metal compounds.

The present invention will be explained in more detail below.

The solid raw material for vaporization used in the present invention may be any organometallic compound that is solid at room temperature and can be used as a raw material for vapor phase growth. Indium compounds such as ruindium, trimethylindium/trimethylarsine adduct, trimethylindium/trimethylphosphine adduct, zinc compounds such as ethylzinc iodide, ethylcyclopentagenylzinc, cyclopentagenylzinc, and aluminum such as methyldichloraluminum compounds, gallium compounds such as methyldidichlorogallium, dimethylchlorogallium, and dimethylbromogallium, biscyclopentagenylmagnesium, and the like.

In addition, examples of carriers that are inert to the solid raw materials for vaporization that support these solid raw materials for vaporization include ceramics such as alumina, silica, mullite, glassy carbon, graphite, potassium titanate, quartz, silicon nitride, boron nitride, and silicon carbide. metals such as stainless steel, aluminum, nickel, and tungsten, fluororesin, glass, etc. are used.

The shape of the carrier is not particularly limited, and may be irregular shape,
Various shapes such as spherical, fibrous, net, coil, and cylindrical shapes are used.

It is preferable for the carrier to have a large specific surface area, and it is preferable that the carrier surface has fine irregularities of about 100 to 2000 μm or that the carrier itself has a large number of pores (voids) rather than a smooth carrier. Examples of such carriers include alumina balls, Raschig rings, Helivac, Dickson packing, stainless steel sintered elements, and Kraswool.

As a method for supporting the solid raw material on the carrier, a conventionally practiced method can be employed.

For example, the carrier and the raw material solid are placed in advance in a rotating container according to the weight ratio, and then heated to melt the raw material solid, and then slowly cooled while rotating and stirring, or the carrier is placed in the heated and melted raw material solid. Any method may be used, such as charging the raw material, then removing excess molten raw material, and then cooling.

When carrying out loading, it is important to remove oxygen, moisture, and other volatile impurities contained in the carrier in advance. If oxygen, moisture, etc. are present on the surface of the carrier, the raw material solid will be altered or contaminated, which will not only impair the quality of the obtained film when used as a raw material for vapor phase growth, but also It becomes impossible to stably supply raw materials for the purpose of To avoid such inconveniences, the carrier is heated in advance to a temperature within the allowable range of the material and vacuum degassed, and then the voids are replaced with an inert gas such as boron or argon. It is recommended that you leave it there.

The amount of the solid raw material supported on the carrier is usually 10 to 100 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the carrier.

If it is less than 10 parts by weight, the amount of raw material solid shown in the container volume is small, so the container must be made larger than necessary, which is not economical.

In addition, when 100 parts by weight or more of the raw material solid is supported on 100 parts by weight of the carrier, the surface area of the solid raw material per packed volume does not become as large as expected compared to the case where the solid material is not supported. The desired effect cannot be obtained sufficiently.

The carrier-supported organometallic compound thus obtained is used as a raw material for vapor phase growth.

FIG. 1 shows an embodiment of a raw material supply device used for vapor phase growth to which an organometallic compound supported on a carrier obtained by the above method is applied, and in the figure, 1 is a container having a curved bottom, and 2 is a container with a curved bottom. A carrier gas inlet, 3 a carrier gas outlet, and 4 an organometallic compound supported on a carrier.

The carrier gas outlet 3 has an opening at the center bottom of the container, and the other end is connected to a vapor phase growth apparatus (not shown). Further, a desired amount of the organometallic compound supported on a carrier is supplied into the container 1 from a supply port (not shown) and layered.

Thereafter, a predetermined amount of carrier gas such as hydrogen gas is supplied from the carrier gas inlet 2, and the carrier gas is transferred from the upper part of the container to the lower part of the container while passing through the gap between the organometallic compounds supported on the carrier. A carrier gas containing an organometallic compound for vapor phase growth at a saturation concentration is supplied to a vapor phase growth apparatus (not shown) through a carrier gas outlet 3.

In the above apparatus, an example of using a container 1 with a curved bottom is described, but if the amount of solid organometallic compound that can be stably used is ignored, it is of course possible to use a container with a straight bottom. It is also possible to disperse the carrier gas outlet ports 3 into a plurality of locations at least at the bottom to relatively stably collect the gas at the saturated concentration, but it is possible to relatively stably collect the gas at the saturated concentration, but it is possible to use a simple device, stabilize the gas at the saturated concentration, and achieve high efficiency. The use of containers with curved bottoms is recommended for ease of use.

In addition, the amount of the carrier-supported organometallic compound to be supplied to the container is normally aimed at the area below the carrier gas inlet, but by dispersing the carrier gas inlet, the carrier gas can be uniformly introduced to the upper part of the carrier-supported organometallic compound stack. This does not apply if the structure is possible.

<Effects of the Invention> According to the present invention detailed above, an organometallic compound that is solid at room temperature used for vapor phase growth is simply supported on a carrier, and this is applied to an organometallic compound supply device for vaporization used for vapor phase growth. By simply adopting this extremely simple method, it is possible to supply organometallic compounds for vapor phase growth with a certain reproducibility to the vapor phase growth apparatus, and as a result, the amount of solid organometallic compounds that can be stably used can be increased. The industrial value of this product is extremely large.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

<Examples> Example 1 100 g of 4mtnφ alumina balls manufactured by Fujimi Abrasives were placed in a two-ring flask with a three-way cock, and vacuum treatment was performed for 2 hours while heating to about 150°C.

Next, this was cooled to room temperature, and 60 g of trimethylindium was charged in a nitrogen gas atmosphere.

The flask was attached to a rotary evaporator and heated to 90-95°C using an oil bath to melt the trimethylindium. When the liquid phase of trimethylindium almost disappeared, the oil bath was removed and the flask was cooled.

The alumina bulb portion was taken out into a separate container under a nitrogen atmosphere and weighed, and the weight of the broken metal was 140 g.

In the same manner, 100 g of Dickson packing was used instead of the alumina balls, and the total weight of Dickson packing after treatment was 128 g.

Example 2 As shown in FIG. 1, the gas inlet is located at the top of the container,
Example 1 was placed in a 38 mm diameter container with a gas outlet opening at the bottom of the container and a valve at each port.
70g of trimethylindium supported on alumina spheres obtained in
I prepared it.

Next, the container was immersed in a constant temperature bath at 20° C., and the outlet side was connected to a cryogenic trap for collecting trimethylindium. Thereafter, hydrogen gas was flowed at 400 cc per minute from the gas introduction side of the container, and the flow was interrupted every 4 hours to measure the weight of trimethylindium collected in the trap.

As a result, until the weight of trimethylindium supported on the alumina spheres reached 4.3 g, the amount of trimethylindium collected per trap was 1.03 to 1.3 g.
It remained in the range of 0.08g.

Similarly, 90 g of trimethylindium supported on the dikun packing obtained in Example 1 was filled into a container with a diameter of 60 mm and measured. Trimethylindium per serving is 1.09-1.12 g
It remained within the range of .

Comparative Example 1 A container with a diameter of 38 mm as used in Example 2 was filled with 50 g of 4φ alumina spheres that had been heated and vacuum treated and 20.0 g of trimethylindium crystal powder, and the whole was shaken up and down to mix them.

This was then vaporized in the same manner as in Example 2, and the weight of the collected trimethylindium was measured.The same amount of collected trimethylindium was obtained in the first to third measurements as in Example 2, but after the third measurement, The weight of trimethylindium in the container is 16.82
Even though the amount was 0.98 g, the amount collected started to decrease from the fourth time, and the amount collected at the fourth time was 0.98 g.

Comparative Example 2 20.0 g of trimethylindium crystal powder with a diameter of 3
The weight of the collected trimethylindium, which was filled into an 8-diameter container and vaporized in the same manner as in Example 2, was measured: 1.01 g for the first time, 0.97 g for the second time, and 0.9 g for the third time.
2g, the fourth time was 0.87g◎

[Brief explanation of the drawing]

Fig. 1 shows an organometallic compound supply device for vapor phase growth filled with the organometallic compound supported on a carrier obtained in the present invention, and Fig. 2 shows an organometallic compound supply device for vapor phase growth filled with an organometallic compound that is liquid at room temperature. In the figure, 1 is a container, 2 is a carrier gas inlet, 3 is a carrier gas outlet, and 4 is an organometallic compound supported on a carrier. Figure 1 Figure 2

Claims (2)

[Claims] (1) A carrier-supported organometallic compound for use in vapor phase growth, characterized in that the organometallic compound is coated on a carrier that is inert to the organometallic compound that is solid at room temperature. (2) In an organometallic compound supply device for vapor phase growth consisting of a container that stores an organometallic compound that is solid at room temperature and sublimates the solid organometallic compound for vaporization, the container has a carrier gas inlet at the top and a carrier gas inlet at the bottom. A gas phase characterized by having a gas outlet and filling the container with a carrier-supported organometallic compound in which the organometallic compound is coated on a carrier inert to the organometallic compound for vaporization. Organometallic compound supply device for growth.